Dicyanodiamide-ammonia condensation products and process for making same



' ably been diluted, are directly employed.

able according to the present invention possess 45 chloride The Patented Aug. 13, 1 946 v j UNITED STATES PATENT 1 OFFICE 2,405,863 1 DICYANODIAMIDEeAMMONIA CONDENSA- TION PRODUCTS AND PROCESS FOR' MAKING SAME' v a j Jules Treboux, vlltiehen, near Basel, Switzerland," assignor to the firm J. R. Geigy A. (l.,'Basel, Switzerland I No Drawing. Application March'25, 1943, .Serial No. 480,567. In Switzerland June 22,1942

10laim. (Cl. 260.-69l:

It has been found that valuable new condensaproducts, is superfluous in the present case, which tion products are obtained by condensing 1 mofact represents a substantial simplification and lecular proportion of dicyanodiamide and at least reduction "of the costs of the process, Besides, r 1 molecular proportion of ammonia, which is generally'weaker concentration of the treating present partly in form of urea and partly in form baths will suifice than when working with the of a mineral acid ammonium salt, with at least 2 above-mentioned similar comparison products. molecular proportions of formaldehyde. Instead The present invention is illustrated by the folof ammonia, amines with primary or secondary lowing examples, wherein the parts are b weight. amino groups may also be used; among the ureas Of course, this invention must not be understood coming into question it is advantageous to use as being limited to the following. examples. those which contain at least one replaceable hy- E l 1 drogen atom at a nitrogen atom, Instead of the 6 dicyanodiamide and of the ureas, it is also pos- 17 parts of dicyanodiamide, 12 parts of urea sible to wholly or partly use quite well compounds and 30 parts of 30% hydrochloric acid are reobtainable by interaction from both the said com- 15 fluxed during 6 hours. Then, at 30 C., 50 parts of pounds, such as for example ammeline and de- 30% formaldehyde are added thereto, the mixture rivatives. The same is the case for the couple: is stirred for 6 hours at 75-85 C, and treated dicyanodiamide plu ammonium salts. Instead with 10 parts of glacial aceti acid. This solution of the latter compounds reaction products of these may be added directly to the after-treating baths components may wholly or partly be used, e. g. used for direct-dyeings,

biguanides, but also compound which are con- When the quantity of the urea used isdeverted into biguanides under the said reaction creased, e. g., down to 6 parts, final products with conditions. Instead of the ammonium salts, the similar properties are obtained which, however, ureas used can be previously hydrolysed by means show somewhat inferior activity for after-treating of mineral acids, thus producing, as is known, direct-dyeings. mineral acid ammonium salts, while splitting off Example 2 carbon dioxide; of course, the latter method is technically much less advantageous.

The new condensation products which serve for improving the fastness properties of direct-dyeings by after-treatment of the dyeings are obtained in form of bright resins which are soluble in water and acids. The best Way consists in that the resulting reaction solutions, if necessary after the addition of acid or after having suit- 34 parts of dicyanodiamide, 18 parts of urea, 5.5 parts of ammonium chloride, '75 parts of water and parts of 30% hydrochloric acid are boiled under reflux for 6 hours, then 80 parts of formaldehyde of 37.4% strength are added and'the whole is heated for 6 hours to 75-85 C. After completion of the condensation the solution is treated with 10 parts of glacial acetic acid.

' If the quantity of the formaldehyde is reduced to 64 parts or the quantity of aldehyde increased to 160 parts, final products with almost identical properties are obtained; in the latter case it is preferable to condense for a longer time.

However, it is already known that the fastness properties of direct-dyeings can be improved by after-treatment with condensation products of aminotriazine with aldehyde. By such a treat- 40 ment there results a deterioration of the light- Example 3 fastness which may be removed by an after-treat- The procedure indicated in Example 2 is fob ment of the dyemgs with C p lowed, but with themodification that there are trarily thereto the condensation products obtainused 12 parts of urea and 11 parts of ammonium o rti of th final roduct are the advantage that they do not unfavourably inpr pe es e p fiuence the light-fastness of the direct-dyeings ldentlcal' Example 4 thus treated and that an after-treatment with copper-salts is superfluous, which after-treat- Condensation is carried out as described in ment cannot be carried out with dyestuifs which Example 2, but there are used 6 parts of urea and are sensitive to copper Furthermore, any heat- 16 parts of ammonium chloride. An identical ing of the dyed and after-treated goods, which product is thus also obtained. is necessary when using similar after-treating agents in order to obtain the complete condensation of the used and low condensed condensation 17 parts of dicyanodiamide, 11 parts of am- Example 5 has completed, that is to say mcnium chloride and 60 parts of water are boiled under reflux for 6 hours. Separately 17 parts of dicyanodiamide, 12 parts of urea and 60 parts of 15% hydrochloric acid are refluxed. Then both solutions are combined, whereupon 80 parts of 37.4% formaldehyde are added thereto and the mixture is heated for'fi hours to 75-85 C. The

solution thus obtained possessesthe same properties as that produced according to Example 1. Example 6 h I 34 parts of dicyanodiamide in 60 parts of 15% hydrochloric acid are boiled under reflux for 6 hours. A solution of 24 parts of urea and 60 parts of hydrochloric acid of 15% strength is added thereto, which solution has been, previously treated in the same manner. Then the mixture.

is treated with 100 parts of 30% formaldehyde and heated to 75'-85 for about 6 hours.

Example 7 34 parts of dicyanodiamide, 24 parts of urea, 200 parts of water and 52 parts of 93% sulfuric C., until the condensation 34 parts of dicyanodiamide, 12 parts of urea and 11 parts of ammonium chloride are added to 120 parts of water, the whole is heated to boiling for 12 hours, then treated with 80 parts of 37.4% formaldehyde and the condensation completed by heating the mixture for 6 hours to 80 C.

What I claim is: V A process for the manufacture of an acid soluble condensation product from dicyanodiamide,

urea, ammonium chloride and formaldehyde, which comprises boiling for several hours sub- 7 stantially one mol of dicyanodiamide with at most one mole of urea in presence of hydrochloric acid, whereby the urea is partly'hydrolyzed to NHiCl, adding at least two molsof formaldehyde and condensing at 75-85 C. r

' JULES TREBOUX. 

